WO1996006801A1

WO1996006801A1 - Sodium percarbonate that is stable and excellent in solubility

Info

Publication number: WO1996006801A1
Application number: PCT/JP1995/001726
Authority: WO
Inventors: Kanji Sato; Shigeki Yoneyama; Yuichiro Yoshinaga
Original assignee: Tokai Denka Kogyo Kabushiki Kaisha
Priority date: 1994-08-30
Filing date: 1995-08-30
Publication date: 1996-03-07
Also published as: JP3764479B2; AU3354395A

Abstract

Sodium percarbonate improved in stability and solubility by coating the same with (A) at least one compound selected from among sulfates and silicates, (B) at least one compound selected from among salts of mono- and dicarboxylic acids bearing four or more carbon atoms, and (C) at least one compound selected from among salts of sulfated oils, α-olefinsulfonic acids and mono- and dialkyl sulfosuccinates.

Description

Specification

Sodium percarbonate with good stability and solubility

Industrial applications

The present invention relates to sodium percarbonate which is stable and excellent in solubility, and particularly to sodium percarbonate which is stable and excellent in solubility and suitable for use as a bleaching agent in detergents and the like.

BACKGROUND OF THE INVENTION

Sodium percarbonate is a solid particulate material, and is widely used as a bleaching agent, a detergent, a bactericide, and the like. Sodium percarbonate as a bleaching agent has excellent solubility at low temperatures, has a high bleaching effect, and is a stable compound under normal storage conditions. However, sodium percarbonate has drawbacks such as being unstable in storage under high humidity conditions and in combination with detergents. In household detergents, products containing a fixed amount of sodium percarbonate as a bleaching agent are particularly desirable. However, zeolite used as a builder in combination with detergents loses its stability when it comes in contact with a small amount of water contained in detergents, and may not only lose the bleaching effect but also deactivate the effectiveness of the detergent. There is. Various proposals have been made to solve these problems.

. For example, in Japanese Patent Publication No. Sho 63-3-56167, a method of coating with a magnesium salt of magnesium sulfonate or a magnesium salt of a sulfate ester is used. A method of further coating a magnesium salt with an alkali or alkaline earth metal sulfate or hydrochloride is disclosed in Japanese Patent Application Laid-Open No. 60-118,606, which discloses boric acid or a partially neutralized borate. And a method of coating with a water repellent, and Japanese Patent Publication No. 59-1940000 discloses a method of coating with a borate and a magnesium compound. Has proposed a method of coating with a surfactant and a mixture of a water-insoluble compound that is compatible with the surfactant. Each of these methods avoids contact with detergent components by coating with a specific chemical. This is a method of stabilizing sodium percarbonate.However, these conventional methods have insufficient stabilizing effects when stored under high-humidity conditions and when compounding detergents, and the deviation is insufficient. It cannot be added.

The present inventors have previously disclosed in JP-A-3-40909, sodium percarbonate, at least one compound selected from the group consisting of monocarboxylic acids having 4 or more carbon atoms, dicarboxylic acids and salts thereof. And a composition comprising at least one compound selected from the group consisting of alkali metal and alkaline earth metal sulfates, nitrates and silicates. This has a drawback that the stability at the time of mixing the detergent is insufficient, but shows a certain effect. The dissolution rate is low, and the solubility is practically insufficient when used in a detergent or the like.

Summary of the Invention

The present inventors have conducted intensive studies to solve the above-mentioned problems. As a result, sodium percarbonate contains (A) at least one compound selected from the group consisting of sulfates and silicates, and (B) carbon atoms of 4 or more. At least one compound selected from the group consisting of mono- and dicarboxylates; and (C) a group selected from the group consisting of sulfated oil salts, sodium olefin sulfonates, monols and di-alkyl sulfosuccinate salts. In addition, the present inventors have found that by coating at least one compound, a remarkably superior effect can be obtained as compared with the prior art, and have led to the present invention.

That is, the present invention provides sodium percarbonate comprising: (A) at least one compound selected from the group consisting of sulfates and silicates; and (B) a group consisting of mono- and di-fluorocarbonates having 4 or more carbon atoms. At least one compound selected from the group consisting of (C) a sulfated oil salt, a haloolefin sulfonate, a mono- and dialkyl sulfosuccinate salt, The present invention provides sodium percarbonate which is significantly improved in stability at the time of blending a detergent as compared with conventional sodium percarbonate, and has excellent solubility. Preferred embodiments of the invention

In the present invention, the salt of the component (A) or constituting the silicate is preferably an alkali metal salt or an alkaline earth metal salt. Examples of sulfates include, for example, sodium sulfate, potassium sulfate, and magnesium sulfate. Examples of silicates include, for example, sodium silicate (No. 1, 2, and 3), sodium mesosilicate, sodium orthosilicate, and the like. And potassium silicate. Particularly, sodium sulfate is preferable.

In the present invention, the carboxylic acid constituting the mono- or di-carboxylate having 4 or more carbon atoms of the component (B) includes, for example, butyric acid, isobutyric acid, valeric acid, cabronic acid, cabrylic acid, acetic acid, and lauric acid. Acids, myristic acid, palmitic acid, stearic acid, isostearic acid, araquinic acid, behenic acid, lignoceric acid, cyclohexancarboxylic acid, crotonic acid, 2-methylacrylic acid, 2-ethylhexylic acid, and solvin Acid, 2,4-pentanedic acid, zomarinic acid, oleic acid, linolenic acid, linoleic acid, ricinoleic acid, gadrenic acid, eric acid, seracoleic acid, benzoic acid, diphenylacetic acid, toluic acid, p-t Butylbenzoic acid, phenylacetic acid, benzoylbenzoic acid, ethylbenzoic acid, 2,3,5-trimethylbenzoic acid, hina Toeic acid, / S-naphthoic acid, 2-methylnaphthoic acid, sebacic acid, pentadecanoic acid, dodecane diacid, brassic acid, tetradecanoic acid, tabsic acid, itaconic acid, muconic acid, naphthenic acid, tallow fatty acid, horse fat fatty acid, Sheep fat fatty acid, lactate fatty acid, coconut oil fatty acid, palm oil fatty acid, palm kernel oil fatty acid, soybean oil fatty acid, linseed oil fatty acid, castor oil fatty acid resistant, rice bran oil fatty acid, rapeseed oil fatty acid, and hydrogenated oils and fats And fatty acids. Usually, a saturated or unsaturated lipoprotective monocarboxylic acid having 8 to 22 carbon atoms is preferred, and a saturated or unsaturated carboxylic acid having 8 to 18 carbon atoms is particularly preferred. (Alkali gold as salt)! Salts or alkaline earth metal salts, such as sodium, potassium, magnesium or calcium salts.

In the present invention, the sulfated oil salt of the component (C) includes, for example, sulfated olive oil, Sulfation using animal and vegetable fats such as sulfated castor oil, sulfated soybean oil, sulfated peanut oil, sulfated cottonseed oil, sulfated rapeseed oil, sulfated rice bran oil, sulfated whale oil, sulfated fish oil and sulfated tallow, etc. There are sodium, potassium, magnesium, and calcium salts of oil. Particularly, a sodium salt of a sulfated castor oil is preferable.

Shed one O Les as preferably fins sulfonate C ₆ - _{3 0} has those obtained by scan sulfonated non Orefuin, this is normally the form of a mixture of alkenyl sulfonate and hydroxyaldehyde alkanesulfonate ing. For example, sodium salt, potassium salt, magnesium salt of α-dodecene sulfonate, α-hexadecene sulfonate, α-octadecene sulfonate and α-eicosene sulfonate, There are calcium salts.

Mono - and as preferably di-alkyl sulfosuccinate ester salts (, - there is, and di-alkyl sulfosuccinate ester le salts and more preferably C ₄ - - 2 0 primary or mono secondary alcohols., ₈ There are mono- and dialkylsulfosuccinates of primary or secondary alcohols, for example, when the alkyl group is methyl, ethyl, propyl, butyl, ybutyl, amiyl, isoamyl, hexyl, cyclohexyl, octyl, Isooctyl, 2-ethylhexyl, nonyl, decyl, lauryl, millisteel, palmityl, stearyl, eicosyl, sodium and potassium salts of dialkylsulfosuccinates which are behenyl groups are salts of sodium, potassium, magnesium and calcium. is there.

In the coating agent of the present invention, sufficient effects can be obtained even when the compounds of the groups (III), (III) and (C) are coated on sodium percarbonate alone or in combination of two types. However, sufficient effects can only be obtained by using the three compounds of the groups (II), (III) and (C) in combination.

For example, when sodium percarbonate is coated with at least one compound selected from the group (ii) and at least one compound selected from the group (ii), washing is performed. Although the stability at the time of compounding is insufficient, a relatively good one can be obtained, but the dissolution rate is slow and practical use is difficult. Only when the compounds of groups (A), (B) and (C) are used together can a compound having good stability and a high dissolution rate be obtained.

The order of coating is not particularly limited, but a method of coating the compound of the group (A) and then mixing and coating the compounds of the groups (B) and (C) is preferable. The mixing ratio of the compound of group (B) and the compound of group (C) is the same when the total amount of the compound of group (B) and the compound of group (C) is the same. When the ratio of the (C) group compound is large, the dissolution rate increases, but the stability tends to decrease. The ratio of the compound of the group (B) in the mixture of the compounds of the groups (B) and (C) is preferably from 10 to 90% by weight, more preferably from 30 to 70% by weight.

The coating amount of the compound (A) is preferably 1 to 30% by weight, more preferably 5 to 20% by weight. The coating amounts of the compounds of the groups (B) and (C) are each preferably 0.1 to 10% by weight, more preferably 0.5 to 5% by weight. (A) Group compound 1? Below, when each of the compounds in the groups (B) and (C) is 0.1% or less, a sufficient effect cannot be obtained. In the case of the compounds in the group (A), 30% or more, and the compounds in the groups (B) and ( When all of the C) group compounds are 10% or more, a sufficient effect can be obtained, but the effective oxygen concentration is reduced more than necessary.

The coating agent of the present invention is preferably provided for coating as a solution with water or an organic solvent. Particularly, an aqueous solution is preferable. The coating method in this case is not particularly limited, but a method capable of adhering a coating agent and rapidly removing the solvent is preferable. A specific example of an apparatus that can be used for such coating is a bancoating apparatus. , Rolling coating equipment, fluid coating equipment, fluid rolling coating equipment, etc. Particularly preferred is a flow coating device.

The coating agent of the present invention can be coated in a slurry form. For example, the compound (A) is made into a slurry, and the compounds (B) and (C) are coated in the form of a solution. It is also possible. It is also possible to coat the (B) group and / or (C) group compound as a solution and add the (A) group compound to this solution in powder form as a slurry.

In coating with a slurry, the finer the component particles, the more effective. The preferred particle size is less than 250; /. As the apparatus that can be used for coating the slurry, any apparatus that can reduce the crushing of sodium percarbonate particles and can coat uniformly can be used.For example, in addition to the above-described coating apparatus, a container rotary mixer, a container fixed shaft rotary mixer, It is also possible to use a multifunction machine that combines both mixers.

The sodium percarbonate to be coated in the present invention is not particularly limited, and any of as-crystal or granulated by granulation can be used. It is preferably in the form of granules. The size of the granules is preferably from 0.1 to 2 mm, particularly preferably from about 0.5 to 1 mm. When granulating into granules, it is a common additive to sodium percarbonate in advance such as sodium carbonate, sodium bicarbonate, sodium gayate, a stabilizer such as chelating agent, and CMC, sodium polyacrylate, etc. A binder and the like can be added. The present invention will be described more specifically with reference to examples and comparative examples, but the present invention is not limited to the examples. In addition, all percentages are weights in terms of pure content, including water of crystallization.

Example

Examples 1 to 4 2

Sodium carbonate and hydrogen peroxide were allowed to react in an aqueous solution, and the formed crystals were separated by centrifugal filtration.The resulting wet sodium percarbonate was added with 3% of sodium carbonate, 0.5% of carboxymethylcellulose as a binder, and 0.5% of carboxymethylcellulose. 0.2% of No. 3 sodium silicate was added, and then the mixture was adjusted to pure water with a water content of 11% and mixed. Next, granules were formed by a horizontal screw extrusion type granulator equipped with a screen having a hole diameter of 0.8 mm, and dried by a fluidized drier. The obtained granules (400 g) were flow-sprayed While blowing hot air at 105 to 110 ° C with a single-stage device, the substances shown in (A) Compounds in Table 1 were formed into an aqueous solution of 10 to 25% and 5 (TC aqueous solution). A predetermined amount was sprayed little by little.

Next, the compounds of the groups (B) and (C) in Table 1 were mixed to form an aqueous solution of 10 to 20 ° C. and 50′C, and a predetermined amount was sprayed little by little to permeate and coat. After spraying, it was dried for 5 minutes. The available oxygen concentration of the obtained sodium percarbonate granules was 11 to 13%. 5 g of the sodium percarbonate granules thus obtained and 45 g of a commercially available linear alkylbenzene sulfonic acid salt-based heavy powder detergent (containing 10% of synthetic zeolite and 3% of water) were thoroughly mixed to give 39 mm0 X 50 ^e C placed in an open container of Boriechiren of 85mmH, 4 5 hours after standing under a relative humidity of 80% to measure the residual available oxygen was calculated stability (available oxygen remaining rate).

The dissolution rate (1 minute) was measured in a 1-liter beaker equipped with a 6 cm stirring blade and a current measurement electrode. C 1 liter of pure water was added, the stirring blade was rotated at 200 rpm, a DC voltage of 2 V was applied, 1 g of the obtained sodium percarbonate granules was charged, and the current value was measured. The dissolution rate per minute was calculated. Table 1 shows the results.

Current value 1 minute after turning on

Dissolution rate = X100% Current value at the time of completion of dissolution Measurement of available oxygen was performed by sodium redoxotium sulfate redox titration method. For comparison, sodium percarbonate granules before coating, those coated with the (A) group, the (B) group and the (C) group compounds alone, and the (A) and (B) group compounds were coated. Table 2 shows the results as comparative examples. table 1

Coating agent

Application stability Dissolution rate

Example (Α) Group compound addition rate (Β) Group compound addition rate (C) Group compound addition rate

Να

1 Sodium sulfate 10 ナ Sodium sulphate 1.5% Sulphated castor 1.5% 90% 100%

Room

2 sodium caprylate 90

3 sodium caprate 92

M

4 sodium laurate 91 oo

M

5 Potassium stearate Sulfated olive oil 91

Κ II r

6 7.0 2.0 95 85

7 Sulfuric acid sodium arachinate 1.5 1.5 89 100

Mm

8 Sodium sulfate sodium oleate 0.5 Sulfated castor oil nato 0.5 84

Mullium

9 1.5 1.5 90

10 Potassium oleate 7.0 Sulfated castor oil 2.0 95 92

Room

Table 1 (continued)

Coating agent

Application stability Dissolution rate

Να

11 Sodium sulfate 15% Sodium oleate 1.5 ¾ Sulfated castor oil nato 1.5% 92% 100%

Mu Lim

12 Magnesium sulfate 5 〃〃〃〃 88 〃

13 No. 3 sodium silicate 3 〃〃〃〃 89 98

14 Sodium metasilicate 5 〃〃〃〃 90 100 O Sodium sulfate 5

15 Potassium gaylate 5 ナ Sulfated soybean oil トリ 90

Room

16 Potassium sulfate 12 Sodium linoleate ゥ 89 〃

Mm

17 Magnesium sulfate 5 Nasyl ricinoleate 〃 Sulfated sodium oil リ 89 〃

Ium

18 Sodium sulfate 10 Potassium behenate 〃 Sulfated beef tallow ゥ 88

M

19 〃カリウム Potassium crotonate 〃〃 92 〃

Table 1 (continued)

Coating agent

Application stability Dissolution rate Example * (Α) Group compound addition rate (Β) Group compound addition rate (C) Group compound addition rate

Να

20 Sodium sulfate 10% 2-Methylacrylic acid 1.5% Sulfated rice bran Shanto 1.5% 90 ¾ 100 ¾

Sodium lithium

21 〃ナ sodium hexylate 〃〃〃 91 〃

M

22 〃〃 2-ethylhexyl sulfated castor oil nato 〃 90

Sodium sodium acid

23 〃〃〃 2 · 0 〃〃 93 〃

24 〃〃〃 0.5 〃 0.5 89 〃 Sodium benzoate モノ Monooctyl sulfo

Sodium succinate

25 〃〃 2-ethylhexyl 0.5 Sulphated castor oil nato 1.5 90 ナトリウム Sodium lime

Sodium oleate

Mm

26 ナ sodium dodecanoic acid 1.5 a-dodesenseulfo 〃 87 〃

Sodium sodium

27 〃〃 Tetra "sodium diacid 〃〃〃 88 〃

Rhium

Table 1 (continued)

Coating agent

Application stability Dissolution rate Example (Α) Group compound addition rate (B) Group compound addition rate (C) Group compound addition rate

Να

Sodium sulfate Go y

Ζο 10% sodium sebacate 1.5% α-hexadesense 1.5% oo ¾ 1UU ¾

ル

Ί £

on Sodium sulfate 8 Sodium benzoate y 〃〃 o ynu

Magnesium sulfate 2 on Potassium sulfate 10 P-Na-toluate 〃 α-octadesence 〃 oo

00

Ruriumuhon Compound

Aluminum salt

31 ~ 7 ~ stream 0. D 89 硫酸 sulfated castor oil nato 0.5

Dream

go Sodium sulphate 10 a—Natodecanoate 〃 monolauryl sulfo oo

1.5

Reno / ~ J1 No People

ヽ Ι ¾¾ί + k Γ I I I Λ ^r nom / No. 1 sodium silicate 2

33 Sodium sulfate 10 Sodium succinate 10 Naphthenate 酸 Dioctyl sulfoco 〃 91 98 m (# 1 25)

34 〃ナ Sodium tallow fatty acid 〃 Monooctyl sulfo 〃 91 100 um Sodium succinate

Table 1 (continued)

Hitoshi IJ

Application stability Dissolution rate Example (A) Group compound addition rate (B) Group compound addition rate (C) Group compound addition rate

35 Sodium sulfate 10% Horse fat fatty acid 1.5% Di-2-ethylhexyl 1.5% 91% 100% Mussyl sulfosuccinic acid

"Sono

Coconut oil fat acid-proof sodium qn

No

Palm oil fatty acid nato dibutylsulfokoha O

RE 'NO NO TOF 7' NO

Soybean oil fatty acid

Room

39 iABSWiBS? 90, 90, 80, 90

Sodium succinate

40 Hydrogenated tallow fatty acid monooctyl sulfo 91

Sodium sodium citrate

41 Castor oil fatty acid nato 90

Rhium

42 Beef tallow soda stone mixture 92

8 0%

Coconut oil

鹼 20% ^J

Table 2

IJ

Comparative stability Dissolution rate Example (Α) Group compound addition rate (Β) Group compound addition rate (C) Group compound addition rate

Να

1% %% 25% 100%

2 Sodium sulfate 10 34 100

3 〃 20 40 100

4 ― sodium stearate 1,5 ― 48 43

Pum

5 1 〃 7.0 1 58 28

6-Monosulfated castor oil nato 2.0 40 100

Lium

7 a-Dodesen Luho 〃 40 〃

Sodium

8 Monooctyl sulfo 〃 42 〃

Sodium succinate

9 Sodium sulfate 10 Sodium stearate 1.5 55 42

Room

Table 2 (continued)

Specific coating agent

Stability ί¾ solution rate Example

Να (Α) Group compound addition rate (B) Group compound addition rate (C) Group compound addition rate

10 ffi w & ui RXiP 10 1 Li 1/0 S az ί t¾i 10 1 it 7 n ¾ 72% 28%

Room

11 〃牛 Tallow soda stone, mixed 7.0 71 25

8 0% -go

Coconut oil soda stone

鹼 20% ^J

12 硫酸 sulfated castor oil nato 2.0 55 100

Rhium

13 〃〃 Monooctyl sulfo 〃 57 100 Sodium succinate

Example 4 3 to 4 5

Predetermined amounts of the (B) group compound and the (C) group compound were measured, the (B) group compound and the (C) group compound were mixed, and a 20% aqueous solution was prepared using the mixture. A predetermined amount of the powdery (A) group compound having a particle diameter of 150 m or less was added to the aqueous solution, and the mixture was mixed well to prepare a slurry.

On the other hand, 3 kg of granular sodium percarbonate obtained by granulation and drying in the same manner as in Examples 1 to 42 was put into a 5-liter 2-shaft ribbon blender and rotated at 40 rpm. The prepared slurry was dropped. After dropping, the mixture was continuously stirred for 5 minutes to coat, and dried with a fluidized drier while blowing hot air at 105 to 110 ° C. The effective oxygen concentration of the obtained sodium percarbonate granules was 12 to 13%. Table 3 shows the results of the stability and the dissolution rate measured in the same manner as in Examples 1 to 42.

Table 3

Infiltration coating

Application stability Dissolution rate Example 17

Να (Α) group compound addition rate (Β) group compound addition rate (C) group compound addition rate (1 minute)

43 Sodium sulphate 12% Olive ¾Natri 1.5 ¾ Sulfated castor oil nato 1.5% 86% 100%

Room

44 ナ sodium hexylate 〃 85 〃

45 〃 2-ethyl 〃〃〃〃 86

Sodium luate

Claims

The scope of the claims

1. From sodium percarbonate, (A) at least one compound selected from the group consisting of sulfates and silicates, and (B) from the group consisting of mono- and di-fluorocarbonates having 4 or more carbon atoms. A stable material coated with at least one compound selected from the group consisting of (C) a sulfated oil salt, a thiophene sulfonate salt, a mono- and dialkyl sulfosuccinate salt; Sodium percarbonate with excellent solubility.

2. Sulfates, silicates, monosulfates, mono-sulfuric acid sulfates, mono-sulfonated olefin sulphonates, monosulfates, and dialkylsulfosuccinates are salts of Alkyllium metal or 2. The sodium percarbonate according to claim 1, which is an alkaline earth metal salt.

3. Any one of claims 1 and 2, wherein component (A) is coated in an amount of from 1 to 30% by weight, and components (B) and (C) are each added in an amount of from 0.1 to 10% by weight of sodium percarbonate. Or sodium percarbonate according to item 1.

4. The sodium percarbonate according to any one of claims 1 to 3, wherein the component (A) is sodium sulfate.

5. The sodium percarbonate according to any one of claims 1 to 4, wherein the component (B) is a sodium salt of a saturated or unsaturated fatty acid having 8 to 18 carbon atoms.

6. The sodium percarbonate according to any one of claims 1 to 5, wherein the component (C) is a sodium salt of a sulfated oil.

7. The sodium percarbonate according to any one of claims 1 to 6, wherein the sodium percarbonate is in a granular form.

8. The sodium percarbonate according to any one of claims 1 to 7, wherein the component (B) and the component (C) are coated in a mixed state after the coating of the (A) clothing.